Bis-Azo Colorants For Use As Bluing Agents

ABSTRACT

This invention relates to bis-azo colorants for use as bluing agents, laundry care compositions comprising bis-azo colorants that may serve as bluing agents, processes for making such bluing agents and laundry care compositions and methods of using the same. The bluing agents are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. These bluing agents are advantageous in providing a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority to and is a continuation of U.S. patentapplication Ser. No. 16/281,248 filed Feb. 21, 2019, which claimspriority to and is a continuation of U.S. patent application Ser. No.15/363,022 filed Nov. 29, 2016, which claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 62/288,482 filed Jan.29, 2016, all of which are hereby entirely incorporated by reference.

TECHNICAL FIELD

This invention relates to bis-azo colorants for use as bluing agents,laundry care compositions comprising bis-azo colorants that may serve asbluing agents, processes for making such bluing agents and laundry carecompositions and methods of using the same. The bluing agents aregenerally comprised of at least two components: at least one chromophorecomponent and at least one polymeric component selected from apolyalkyleneoxy and a capped polyalkyleneoxy. These bluing agents areadvantageous in providing a whitening effect to fabrics.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. Thus, the purpose of bluing agents is generallyto maintain the whiteness perception of these textile substrates andcounteract the fading and yellowing of the substrates. Typically, bluingagents may be found in laundry detergents, fabric softeners, or rinseaids and are therefore applied to textile substrates during thelaundering process. However, it is important that bluing agents functionto improve the whiteness perception of treated textile substrateswithout causing undesirable staining of the textile substrates.Cellulosic substrates, in particular, tend to exhibit a yellow hue afterexposure to light, air, and/or soiling. This yellowness is oftendifficult to reverse by normal laundering procedures. As a result, thereexists a need for improved bluing agents which are capable ofeliminating the yellowness exhibited by ageing cellulosic substrates. Byutilizing such improved bluing agents, the life of the textilesubstrates, such as clothing articles, table linens, etc., may beextended. Domestic washes contain a mixture of fabric types and in theapplication of bluing agents care must be taken so that dye build updoes not occur on fabric types other than cotton. Unfortunately, currentbluing agents that deposit efficiently on cotton can deposit toostrongly on nylon, especially at higher temperatures, thus over hueingthe treated situs over multiple treatment cycles. There is a thuscontaining need for bluing agents that have improved selectivity fordeposition on cotton over other fabric types, such as nylon.

The present invention offers advantages over previous efforts in thisarea, as this invention takes advantage of compounds having anon-sulfonic acid substituent in either the terminal and/or centralphenyl ring of the bis-azo structure. Sulfonic acid groups are known topromote the deposition and staining of acid dyes on cellulosic fabrics.These groups are also essential for the solubility and compatibility ofthe dyes in laundry formulations. While it is necessary that bluingagents deposit from wash water, it is undesirable that they stain thefabric by inadvertent contact or by building up over time, i.e.overhueing. Applicants recognized that modification or replacement ofthe sulfonic acid group at the phenyl terminal end of the bis-azo with anonionic solubilizing group allows for good deposition of the bis-azobut attenuates its staining and overhueing tendencies and still allowsthe bluing agent to be compatible in laundry formulations. Applicantsfurther recognized that the selection of the terminal couplersignificantly impacts the selectivity ratio and enables the intentionalconstruction of dyes highly selective for cotton over nylon. In short,Applicants recognized the source of the current hueing deficiencies andherein provide the solution to such problem. The hueing compoundsdisclosed herein also absorb light at a wavelength appropriate toneutralize the yellowness of cellulosic substrates. These compoundsfunction ideally as bluing agents for cellulosic substrates and may beincorporated into laundry care compositions for use by consumers.

SUMMARY OF INVENTION

This invention relates to laundry care compositions comprising bis-azocolorants that may serve as bluing agents, processes for making suchlaundry care compositions and methods of using the same. The bluingagents are generally comprised of at least two components: at least onechromophore component and at least one polymeric component selected froma polyalkyleneoxy and a capped polyalkyleneoxy. These bluing agents areadvantageous in providing a whitening effect to fabrics, while notbuilding up over time and causing undesirable blue discoloration to thetreated fabrics.

DETAILED DESCRIPTION

As used herein, the term “alkoxy” is intended to include C₁-C₆ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the terms “alkyl” and “alkyl capped” are intended toinclude C₁-C₆ alkyl groups.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions.

As used herein, the term “fabric treatment composition” includes, unlessotherwise indicated, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions and combinations thereof.Such compositions may be, but need not be rinse added compositions.

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof.

Articles formed from cellulosic fibers include textile articles such asfabrics. Articles formed from pulp include paper.

As used herein, the articles including “the”, “a” and “an” when used ina claim, are understood to mean one or more of what is claimed ordescribed.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the terms “polyalkyleneoxy” and “polyoxyalkylene” aremeant to be interchangeable.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

Suitable Bluing Agents

The bluing agents employed in the present laundry care compositions maybe dyes, pigments, or polymeric colorants comprising a chromophoreconstituent and a polymeric constituent covalently bound to one another.The chromophore constituent is characterized in that it absorbs light inthe wavelength range of blue, red, violet, purple, or combinationsthereof upon exposure to light. In one aspect, the chromophoreconstituent exhibits an absorbance spectrum maximum from about 520nanometers to about 640 nanometers in water and/or methanol, and inanother aspect, from about 560 nanometers to about 610 nanometers inwater and/or methanol.

Examples of suitable polymeric constituents include polyoxyalkylenechains having multiple repeating units. In one aspect, the polymericconstituents include polyoxyalkylene chains having from 2 to about 30repeating units, from 2 to about 20 repeating units, from 2 to about 10repeating units or even from about 3 or 4 to about 6 repeating units.Non-limiting examples of polyoxyalkylene chains include ethylene oxide,propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

In one aspect, the bluing agent employed in the present laundry carecompositions may be selected from the following general structures(I-IV):

and mixtures thereof;

-   -   wherein:    -   R¹ is selected from H, alkyl, hydroxyalkyl, polyalkyleneoxy and        capped polyalkyleneoxy; R² and R³ are independently selected        from the group consisting of H, alkyl, alkoxy, alkyleneoxy,        capped alkyleneoxy, polyalkyleneoxy and capped polyalkyleneoxy;        R⁴ is selected from H, C(O)H and C(O)R⁵; wherein R⁵ is        independently selected from the group consisting of C₁₋₇ alkyl,        C₆₋₁₀ aryl, and C₇₋₁₁ arylalkyl; wherein said capping groups are        independently selected from C(O)R⁵ and R⁵; wherein the A ring        may be further substituted with one or more groups selected from        the group consisting of C₁₋₈ alkyl, C₁₋₈ alkoxy, nitro and OR⁶;        wherein R⁶ is selected from the group consisting of H,        hydroxyalkyl, a polyalkyleneoxy and a capped polyalkyleneoxy;        wherein each M is independently selected from the group        consisting of an alkali metal cation, an ammonium ion and an        alkaline earth metal cation.    -   In one aspect, said bluing agent may comprise a polyoxyalkylene        chain having from 2 to about 100 repeating units.    -   In one aspect, said bluing agent may comprise a polyoxyalkylene        chain having from 2 or even 4 to about 50 repeating units    -   In one aspect, said bluing agent may comprise a polyoxyalkylene        chain having from 2 or even 4 to about 30 repeating units.    -   In one aspect, said bluing agent may comprise a polyoxyalkylene        chain having from 2 or even 4 to about 20 repeating units.    -   In one aspect, said bluing agent may comprise a polyoxyalkylene        chain having from 2 or even 4 to about 10 repeating units.    -   In one aspect, bluing agent may comprise a polyoxyalkylene chain        having from about 4 to about 6 repeating units.    -   In one aspect, bluing agent may comprise an alkoxylated bis-azo        polymeric colorant.    -   In one aspect, bluing agent's chromophore may exhibit an        absorbance spectrum maximum in water of from about 520        nanometers to about 640 nanometers.    -   In one aspect, said bluing agent's chromophore may exhibit an        absorbance spectrum maximum in water of from about 560        nanometers to about 610 nanometers.    -   In one aspect, said bluing agent may exhibit an absolute hue        angle in the range of 220° to 320°.    -   In aspect said, bluing agent may exhibit an absolute hue angle        in the range of 240° to 310°.    -   In aspect said, bluing agent may exhibit an absolute hue angle        in the range of 250° to 300°.    -   As will be appreciated by those skilled in the art, the above        noted bluing agents will typically also include additional        bluing agent compounds present at levels that are unlikely to        significantly impact the above bluing agent's performance, as        perceived by the average consumer. Such additional bluing agent        compounds derive from the reagents, impurities therein, and the        synthetic pathway employed to prepare the above noted bluing        agents, as is well known to the ordinarily skilled artisan.        Non-limiting examples of additional bluing agents, which could        be classified as expected impurities, have been disclosed for        other azo dye bluing agents, for example in U.S. patent        application Ser. Nos. 14/747,099 and 14/877,060, which may be        instructive to the unskilled artisan in understanding the nature        of such additional bluing agents that could be expected in the        instant invention. As will further be appreciated, when the        additional bluing agent compounds are present at levels that may        impact the above noted bluing agent's performance, as perceived        by the average consumer, such additional bluing agent compounds        may be removed or retained as desired.    -   By way of example, those skilled in the art realize that        coupling reactions using H-acid derivatives can occur at two        positions, with products represented by structures (II)        and (III) above. For the purposes of the present invention, it        is understood that compounds incorporating H-acid derivatives        represented herein by one particular regioisomer are intended to        include the alternate regioisomer as well. That is, any        particular structure such as (II) above is intended to also        disclose structure (III).    -   In one aspect of the invention, suitable bluing agents include,        but are not limited to the following structures:

A suitable synthesis route for certain bis-azo colorants disclosedherein is shown below:

Wherein R¹ is selected from H, alkyl, hydroxyalkyl, polyalkyleneoxy andcapped polyalkyleneoxy; R² and R³ are independently selected from thegroup consisting of H, alkyl, alkoxy, alkyleneoxy, capped alkyleneoxy,polyalkyleneoxy and capped polyalkyleneoxy; R⁴ is selected from H, C(O)Hand C(O)R⁵; wherein R⁵ is independently selected from the groupconsisting of C₁₋₇ alkyl, C₆₋₁₀ aryl, and C₇₋₁₁ arylalkyl; wherein saidcapping groups are independently selected from C(O)R⁵ and R⁵. Similarrelated approaches may be employed when utilizing H-acid or chromotropicacid derivatives, as are well known in the art.

Suitable starting materials for the A ring include, but are not limitedto, nitrophenols such as 5-methoxy-2-nitrophenol,4-nitro-1,3-benzenediol, 4-methoxy-6-nitro-1,3-benzenediol,5-methyl-2-nitrophenol, 3-methyl-4-nitrophenol, 3-methoxy-4-nitrophenol,2,5-dimethyl-4-nitrophenol, 2,3-dimethyl-4-nitrophenol,4-methyl-5-nitro-1,2-benzenediol, and 2-methyl-4-nitro-1,3-benzenediol,available from Sigma-Aldrich (St. Louis, Mo., USA), BOC Sciences(Shirley, N.Y., USA) or Arch Bioscience Company (West Chester, Pa.,USA), which can be converted to polyalkyleneoxy substituted anilinecompounds by well known procedures.

Suitable starting materials for the central ring (denoted as B in thescheme above) include, but are not limited to, nitrophenols such as2-nitro-1,4-benzenediol, 4-methoxy-3-nitrophenol,4-methoxy-2-nitrophenol, which can be converted through procedures wellknown in the art to suitably substituted benzeneamines. Such substitutednitrophenols can be converted to substituted polyalkoxylatedbenzenamines by well-known literature procedures. For example,4-methoxy-3-nitrophenol or 4-methoxy-2-nitrophenol can be reacted withmono-choropolyalkoxy glycols or simple ethylene oxide in presence of asuitable base to produce alkoxylated substituted nitrobenzenes, whichcan then be reduced using a suitable reducing agent (Hydrogen over RaneyNickel) to produce substituted alkoxylated benzeneamines. Other suitablestarting materials for the central ring include, but are not limited to,benzeneamines such as 2-ethyl-5-methoxybenzenamine,5-ethoxy-2-methoxybenzenamine, 2-ethoxy-5-ethylbenzenamine,2-ethoxy-5-methoxybenzenamine, 2,5-diethylbenzenamine,5-ethoxy-2-methylbenzenamine, 5-ethyl-2-methoxybenzenamine,5-methoxy-2-methylbenzenamine, 5-ethyl-2-methylbenzenamine,2-ethoxy-5-methylbenzenamine, 2-ethyl-5-methylbenzenamine,3-ethoxybenzenamine, 3-ethylbenzenamine, 2-ethylbenzenamine,3-methoxybenzenamine, 2-methoxy-5-methylbenzenamine,3-methylbenzenamine, 2,5-dimethoxybenzenamine, 2,5-dimethylbenzenamine,2-methylbenzenamine, 2,5-diethoxybenzenamine, 2-ethoxybenzenamine,2-methoxybenzenamine, and benzenamine. Such nitrophenols andbenezeneamines are available from Sigma-Aldrich (St. Louis, Mo., USA),or Aurora Fine Chemicals LLC, San Diego, Calif., USA.

Specifically bis-azo colorants denoted above as BA-33, BA-34 and BA-35can be synthesized using the synthetic route shown below:

R⁶ is selected from OH, NH₂ and NHC(O)R⁷; wherein R⁷ is independentlyselected from the group consisting of C₁₋₇ alkyl, C₆₋₁₀ aryl, and C₇₋₁₁arylalkyl.

Alternatively, the bis-azo colorants disclosed herein may be madeaccording to various procedures known in the art and/or in accordancewith the examples of the present invention. For example, the firstcoupling may be carried out using polyalkyleneoxy substituted anilinecompounds derived by known procedures from starting materials such as4-methyoxy-2-nitrophenol or 4-methyl-2-nitrophenol, or 4-aminophenolwhich are available from VWR International, LLC (West Chester, Pa.,USA).

Laundry Care Compositions

Any of the bluing agents described in the present specification may beincorporated into laundry care compositions including but not limited tolaundry detergents and fabric care compositions. The laundry carecompositions including laundry detergents may be in solid or liquidform, including a gel form. Such compositions may comprise one or moreof said bluing agents and a laundry care ingredient. The bluing agentsmay be added to substrates using a variety of application techniques.For instance, for application to cellulose-containing textilesubstrates, the bluing agent may be included as a component of a laundrydetergent. Thus, application to a cellulose-containing textile substrateactually occurs when a consumer adds laundry detergent to a washingmachine. The bluing agent may be present in the laundry detergentcomposition in an amount from about 0.00001% to about 15% by weight ofthe composition, from about 0.0001% to about 10% by weight of thecomposition, from about 0.0001% to about 5% by weight of thecomposition, from about 0.0001% to about 1% by weight of thecomposition, and even from about 0.0001% to about 0.5% by weight of thecomposition.

The laundry detergent composition typically comprises a surfactant in anamount sufficient to provide desired cleaning properties. In one aspect,the laundry detergent composition may comprise, based on total laundrydetergent composition weight, from about 5% to about 90% of thesurfactant, from about 5% to about 70% of the surfactant, or even fromabout 5% to about 40% of the surfactant. The surfactant may compriseanionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants.In one aspect, the detergent composition comprises anionic surfactant,nonionic surfactant, or mixtures thereof.

-   -   Fabric care compositions are typically added in the rinse cycle,        which is after the detergent solution has been used and replaced        with the rinsing solution in typical laundering processes. The        fabric care compositions disclosed herein may be comprise a        rinse added fabric softening active and a suitable bluing agent        as disclosed in the present specification.    -   The fabric care composition may comprise, based on total fabric        care composition weight, from about 1% to about 90%, or from        about 5% to about 50% fabric softening active. The bluing agent        may be present in the fabric care composition in an amount from        about 0.5 ppb to about 50 ppm, or from about 0.5 ppm to about 30        ppm.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, thenon-limiting list of laundry care ingredients illustrated hereinafterare suitable for use in the laundry care compositions and may bedesirably incorporated in certain aspects of the invention, for exampleto assist or enhance performance, for treatment of the substrate to becleaned, or to modify the aesthetics of the composition as is the casewith perfumes, colorants, dyes or the like. It is understood that suchingredients are in addition to the components that were previouslylisted for any particular aspect. The total amount of such adjuncts mayrange, once the amount of dye is taken into consideration from about 90%to about 99.99999995% by weight of the laundry care composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable laundry care ingredients include, but are not limited to,fabric softening actives, polymers, for example cationic polymers,surfactants, builders, chelating agents, dye transfer inhibiting agents,dispersants, enzymes, and enzyme stabilizers, catalytic materials,organic and inorganic opacifiers, bleach activators, polymericdispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfume and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. In addition tothe disclosure below, suitable examples of such other adjuncts andlevels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and6,326,348 B1 that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants'laundry care compositions. Thus, certain aspects of Applicants'compositions do not contain one or more of the following adjunctsmaterials: fabric softening actives, bleach activators, surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic metal complexes, polymericdispersing agents, clay and soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfumes and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. However, whenone or more adjuncts are present, such one or more adjuncts may bepresent as detailed below:

Surfactants

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C₁₀-C₁₆alkyl benzene sulfonic acids, or C₁₁-C₁₄ alkyl benzene sulfonic acids.In one aspect, the alkyl group is linear and such linear alkyl benzenesulfonates are known as “LAS”. Alkyl benzene sulfonates, andparticularly LAS, are well known in the art. Such surfactants and theirpreparation are described for example in U.S. Pat. Nos. 2,220,099 and2,477,383. Especially useful are the sodium and potassium linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄,e.g., C₁₂, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In one aspect, R′ isC₁₀-C₁₈ alkyl, n is from about 1 to 15, and M is sodium, potassium,ammonium, alkylammonium, or alkanolammonium. In one aspect, R′ is aC₁₂-C₁₆, n is from about 1 to 6 or even from about 1 to about 3 and M issodium, potassium, ammonium, alkylammonium, or alkanolammonium, and, inone embodiment, is sodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoxylated, e.g., non-ethoxylated,alkyl ether sulfate surfactants are those produced by the sulfation ofhigher C₈-C₂₀ fatty alcohols. Conventional primary alkyl sulfatesurfactants have the general formula: ROSO₃-M⁺ wherein R is typically alinear C₈-C₂₀ hydrocarbyl group, which may be straight chain or branchedchain, and M is a water-solubilizing cation. In one aspect, R is aC₁₀-C₁₅ alkyl, and M is alkali metal, more specifically R is C₁₂-C₁₄ andM is sodium.

Specific, non-limiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primaryand branched-chain alkyl sulfates (AS); c) C₁₀-C₁₈ secondary (2,3) alkylsulfates having suitable cations including sodium, potassium, ammonium,and mixtures thereof; d) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) whereinx is from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylates in one aspect,comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates asdiscussed in U.S. Pat. Nos. 6,020,303 and 6,060,443; g) mid-chainbranched alkyl alkoxy sulfates as discussed in U.S. Pat. Nos. 6,008,181and 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed inWO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; i) methyl estersulfonate (MES); and j) alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. In one aspect, for use in the liquid detergentproducts herein are those nonionic surfactants which are normallyliquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.In one aspect, R¹ is an alkyl group, which may be primary or secondary,that comprises from about 9 to 15 carbon atoms, from about 12 to 15carbon atoms, or from about 10 to 14 carbon atoms. In one aspect, thealkoxylated fatty alcohols will also be ethoxylated materials thatcontain from about 2 to 12 ethylene oxide moieties per molecule, fromabout 3 to 10 ethylene oxide moieties per molecule, or from about 7 to 9ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17 from about 6 to 15, orfrom about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants havebeen marketed under the tradenames Neodol and Dobanol by the ShellChemical Company.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20, 10 to 16carbon atoms, or is a C₁₂-C₁₆ primary alkyl. R′ is a short-chain moiety,in one aspect R′ may be selected from hydrogen, methyl and —CH₂OH. Whenx+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy andBO is butyleneoxy. Amine oxide surfactants are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x if from 1-30, as discussed in U.S.Pat. Nos. 6,153,577, 6,020,303 and 6,093,856; f) Alkylpolysaccharides asdiscussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 26, 1986;specifically alkylpolyglycosides as discussed in U.S. Pat. Nos.4,483,780 and 4,483,779; g) Polyhydroxy fatty acid amides as discussedin U.S. Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, andWO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactantsas discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (in one aspect C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate wherethe alkyl group can be C₈ to C₁₈, or C₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents comprises at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one comprises an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

Aqueous, Non-Surface Active Liquid Carrier

As noted, the laundry care compositions may be in the form of a solid,either in tablet or particulate form, including, but not limited toparticles, flakes, sheets, or the like, or the compositions may be inthe form of a liquid. The liquid detergent compositions may comprise anaqueous, non-surface active liquid carrier. Generally, the amount of theaqueous, non-surface active liquid carrier employed in the compositionsherein will be effective to solubilize, suspend or disperse thecomposition components. For example, the liquid detergent compositionsmay comprise, based on total liquid detergent composition weight, fromabout 5% to about 90%, from about 10% to about 70%, or from about 20% toabout 70% of the aqueous, non-surface active liquid carrier.

The most cost effective type of aqueous, non-surface active liquidcarrier is typically water. Accordingly, the aqueous, non-surface activeliquid carrier component will generally be mostly, if not completely,comprised of water. While other types of water-miscible liquids, suchalkanols, diols, other polyols, ethers, amines, and the like, haveconventionally been added to liquid detergent compositions asco-solvents or stabilizers, for purposes of the present invention, theutilization of such water-miscible liquids typically is minimized tohold down composition cost. Accordingly, the aqueous liquid carriercomponent of the liquid detergent products herein will generallycomprise water present in concentrations ranging from about 5% to about90%, or from about 5% to about 70%, by weight of the liquid detergentcomposition.

Bleaching Agents

-   -   Bleaching Agents—The cleaning compositions of the present        invention may comprise one or more bleaching agents. Suitable        bleaching agents other than bleaching catalysts include        photobleaches, bleach activators, hydrogen peroxide, sources of        hydrogen peroxide, pre-formed peracids and mixtures thereof. In        general, when a bleaching agent is used, the compositions of the        present invention may comprise from about 0.1% to about 50% or        even from about 0.1% to about 25% bleaching agent by weight of        the subject cleaning composition. Examples of suitable bleaching        agents include:    -   (1) photobleaches for example sulfonated zinc phthalocyanine;    -   (2) preformed peracids: Suitable preformed peracids include, but        are not limited to, compounds selected from the group consisting        of percarboxylic acids and salts, percarbonic acids and salts,        perimidic acids and salts, peroxymonosulfuric acids and salts,        for example, Oxzone®, and mixtures thereof. Suitable        percarboxylic acids include hydrophobic and hydrophilic peracids        having the formula R—(C═O)O—O-M wherein R is an alkyl group,        optionally branched, having, when the peracid is hydrophobic,        from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and,        when the peracid is hydrophilic, less than 6 carbon atoms or        even less than 4 carbon atoms; and M is a counterion, for        example, sodium, potassium or hydrogen;    -   (3) sources of hydrogen peroxide, for example, inorganic        perhydrate salts, including alkali metal salts such as sodium        salts of perborate (usually mono- or tetra-hydrate),        percarbonate, persulphate, perphosphate, persilicate salts and        mixtures thereof. In one aspect of the invention the inorganic        perhydrate salts are selected from the group consisting of        sodium salts of perborate, percarbonate and mixtures thereof.        When employed, inorganic perhydrate salts are typically present        in amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the        overall composition and are typically incorporated into such        compositions as a crystalline solid that may be coated. Suitable        coatings include, inorganic salts such as alkali metal silicate,        carbonate or borate salts or mixtures thereof, or organic        materials such as water-soluble or dispersible polymers, waxes,        oils or fatty soaps; and    -   (4) bleach activators having R—(C═O)-L wherein R is an alkyl        group, optionally branched, having, when the bleach activator is        hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon        atoms and, when the bleach activator is hydrophilic, less than 6        carbon atoms or even less than 4 carbon atoms; and L is leaving        group. Examples of suitable leaving groups are benzoic acid and        derivatives thereof—especially benzene sulphonate. Suitable        bleach activators include dodecanoyl oxybenzene sulphonate,        decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or        salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate,        tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene        sulphonate (NOBS). Suitable bleach activators are also disclosed        in WO 98/17767. While any suitable bleach activator may be        employed, in one aspect of the invention the subject cleaning        composition may comprise NOBS, TAED or mixtures thereof.    -   When present, the peracid and/or bleach activator is generally        present in the composition in an amount of from about 0.1 to        about 60 wt %, from about 0.5 to about 40 wt % or even from        about 0.6 to about 10 wt % based on the composition. One or more        hydrophobic peracids or precursors thereof may be used in        combination with one or more hydrophilic peracid or precursor        thereof.    -   The amounts of hydrogen peroxide source and peracid or bleach        activator may be selected such that the molar ratio of available        oxygen (from the peroxide source) to peracid is from 1:1 to        35:1, or even 2:1 to 10:1.    -   Bleach Boosting Compounds—The compositions herein may comprise        one or more bleach boosting compounds. Bleach boosting compounds        provide increased bleaching effectiveness in lower temperature        applications. The bleach boosters act in conjunction with        conventional peroxygen bleaching sources to provide increased        bleaching effectiveness. This is normally accomplished through        in situ formation of an active oxygen transfer agent such as a        dioxirane, an oxaziridine, or an oxaziridinium. Alternatively,        preformed dioxiranes, oxaziridines and oxaziridiniums may be        used.

Among suitable bleach boosting compounds for use in accordance with thepresent invention are cationic imines, zwitterionic imines, anionicimines and/or polyionic imines having a net charge of from about +3 toabout −3, and mixtures thereof. These imine bleach boosting compounds ofthe present invention include those of the general structure:

-   -   where R¹-R⁴ may be a hydrogen or an unsubstituted or substituted        radical selected from the group consisting of phenyl, aryl,        heterocyclic ring, alkyl and cycloalkyl radicals.

Suitable bleach boosting compounds include zwitterionic bleach boosterszwitterionic bleach boosters, which are described in U.S. Pat. Nos.5,576,282 and 5,718,614. Other bleach boosting compounds includecationic bleach boosters described in U.S. Pat. Nos. 5,360,569;5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351,WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen sourceemployed in the present invention may comprise any of these well knownsources, including peroxygen compounds as well as compounds, which underconsumer use conditions, provide an effective amount of peroxygen insitu. The peroxygen source may include a hydrogen peroxide source, thein situ formation of a peracid anion through the reaction of a hydrogenperoxide source and a bleach activator, preformed peracid compounds ormixtures of suitable peroxygen sources. Of course, one of ordinary skillin the art will recognize that other sources of peroxygen may beemployed without departing from the scope of the invention. The bleachboosting compounds, when present, are typically employed in conjunctionwith a peroxygen source in the bleaching systems of the presentinvention.

-   -   Enzyme Bleaching—Enzymatic systems may be used as bleaching        agents. The hydrogen peroxide may also be present by adding an        enzymatic system (i.e. an enzyme and a substrate therefore)        which is capable of generating hydrogen peroxide at the        beginning or during the washing and/or rinsing process. Such        enzymatic systems are disclosed in EP Patent Application        91202655.6 filed Oct. 9, 1991.

The present invention compositions and methods may utilize alternativebleach systems such as ozone, chlorine dioxide and the like. Bleachingwith ozone may be accomplished by introducing ozone-containing gashaving ozone content from about 20 to about 300 g/m³ into the solutionthat is to contact the fabrics. The gas:liquid ratio in the solutionshould be maintained from about 1:2.5 to about 1:6. U.S. Pat. No.5,346,588 describes a process for the utilization of ozone as analternative to conventional bleach systems and is herein incorporated byreference.

In one aspect, the fabric softening active (“FSA”) is a quaternaryammonium compound suitable for softening fabric in a rinse step. In oneaspect, the FSA is formed from a reaction product of a fatty acid and anaminoalcohol obtaining mixtures of mono-, di-, and, in one aspect,triester compounds. In another aspect, the FSA comprises one or moresoftener quaternary ammonium compounds such, but not limited to, as amonoalkyquaternary ammonium compound, a diamido quaternary compound anda diester quaternary ammonium compound, or a combination thereof. In oneaspect of the invention, the FSA comprises a diester quaternary ammonium(hereinafter “DQA”) compound composition. In certain aspects of thepresent invention, the DQA compounds compositions also encompasses adescription of diamido FSAs and FSAs with mixed amido and ester linkagesas well as the aforementioned diester linkages, all herein referred toas DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA in the present CFSCincludes a compound comprising the formula:

{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R₁]_(m)}X⁻

-   -   wherein each R substituent is either hydrogen, a short chain        C₁-C₆, for example C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl, ethyl, propyl, hydroxyethyl, and the like, poly (C₂₋₃        alkoxy), for example. polyethoxy, group, benzyl, or mixtures        thereof; each m is 2 or 3; each n is from 1 to about 4, or 2;        each Y is —O—(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR— and it is        acceptable for each Y to be the same or different; the sum of        carbons in each R¹, plus one when Y is —O—(O)C— or —NR—C(O)—, is        C₁₂-C₂₂, or C₁₄-C₂₀, with each R¹ being a hydrocarbyl, or        substituted hydrocarbyl group; it is acceptable for R¹ to be        unsaturated or saturated and branched or linear and in one        aspect it is linear; it is acceptable for each R¹ to be the same        or different and typically these are the same; and X⁻ can be any        softener-compatible anion, suitable anions include, chloride,        bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and        nitrate, in one aspect the anions are chloride or methyl        sulfate. Suitable DQA compounds are typically made by reacting        alkanolamines such as MDEA (methyldiethanolamine) and TEA        (triethanolamine) with fatty acids. Some materials that        typically result from such reactions include        N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or        N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium        methylsulfate wherein the acyl group is derived from animal        fats, unsaturated, and polyunsaturated, fatty acids, e.g.,        tallow, hardened tallow, oleic acid, and/or partially        hydrogenated fatty acids, derived from vegetable oils and/or        partially hydrogenated vegetable oils, such as, canola oil,        safflower oil, peanut oil, sunflower oil, corn oil, soybean oil,        tall oil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in U.S. Pat.No. 5,759,990 at column 4, lines 45-66. In one aspect, the FSA comprisesother actives in addition to DQA (1) or DQA. In yet another aspect, theFSA comprises only DQA (1) or DQA and is free or essentially free of anyother quaternary ammonium compounds or other actives. In yet anotheraspect, the FSA comprises the precursor amine that is used to producethe DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:

[R_(4-m)—N⁽⁺⁾—R¹ _(m)]A⁻

-   -   wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, or C₁₄-C₂₀, but        no more than one being less than about C₁₂ and then the other is        at least about 16, hydrocarbyl, or substituted hydrocarbyl        substituent, for example, C₁₀-C₂₀ alkyl or alkenyl (unsaturated        alkyl, including polyunsaturated alkyl, also referred to        sometimes as “alkylene”), in one aspect C₁₂-C₁₈ alkyl or        alkenyl, and branch or unbranched. In one aspect, the Iodine        Value (IV) of the FSA is from about 1 to 70; each R is H or a        short chain C₁-C₆, or C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl, ethyl, propyl, hydroxyethyl, and the like, benzyl, or        (R² O)₂₋₄H where each R² is a C₁₋₆ alkylene group; and A⁻ is a        softener compatible anion, suitable anions include chloride,        bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or        nitrate; in one aspect the anions are chloride or methyl        sulfate.

Examples of these FSAs include dialkydimethylammonium salts anddialkylenedimethylammonium salts such as ditallowdimethylammonium andditallowdimethylammonium methylsulfate. Examples of commerciallyavailable dialkylenedimethylammonium salts usable in the presentinvention are di-hydrogenated tallow dimethyl ammonium chloride andditallowdimethyl ammonium chloride available from Degussa under thetrade names Adogen® 442 and Adogen® 470 respectively. In one aspect, theFSA comprises other actives in addition to DTTMAC. In yet anotheraspect, the FSA comprises only compounds of the DTTMAC and is free oressentially free of any other quaternary ammonium compounds or otheractives.

In one aspect, the FSA comprises an FSA described in U.S. Pat. Pub. No.2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79. In another aspect, the FSA is one described in U.S.Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith et al.,on paragraphs 26-31; or U.S. Pat. No. 6,494,920, at column 1, line 51 etseq. detailing an “esterquat” or a quaternized fatty acidtriethanolamine ester salt.

In one aspect, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one aspect, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another aspect of the invention provides for a rinse added fabricsoftening composition further comprising a cationic starch. Cationicstarches are disclosed in US 2004/0204337 A1. In one aspect, the rinseadded fabric softening composition comprises from about 0.1% to about 7%of cationic starch by weight of the fabric softening composition. In oneaspect, the cationic starch is HCP401 from National Starch.

-   -   Builders—The compositions of the present invention can comprise        one or more detergent builders or builder systems. When present,        the compositions will typically comprise at least about 1%        builder, or from about 5% or 10% to about 80%, 50%, or even 30%        by weight, of said builder. Builders include, but are not        limited to, the alkali metal, ammonium and alkanolammonium salts        of polyphosphates, alkali metal silicates, alkaline earth and        alkali metal carbonates, aluminosilicate builders        polycarboxylate compounds. ether hydroxypolycarboxylates,        copolymers of maleic anhydride with ethylene or vinyl methyl        ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and        carboxymethyl-oxysuccinic acid, the various alkali metal,        ammonium and substituted ammonium salts of polyacetic acids such        as ethylenediamine tetraacetic acid and nitrilotriacetic acid,        as well as polycarboxylates such as mellitic acid, succinic        acid, oxydisuccinic acid, polymaleic acid, benzene        1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and        soluble salts thereof.    -   Chelating Agents—The compositions herein may also optionally        contain one or more copper, iron and/or manganese chelating        agents. If utilized, chelating agents will generally comprise        from about 0.1% by weight of the compositions herein to about        15%, or even from about 3.0% to about 15% by weight of the        compositions herein.    -   Dye Transfer Inhibiting Agents—The compositions of the present        invention may also include one or more dye transfer inhibiting        agents. Suitable polymeric dye transfer inhibiting agents        include, but are not limited to, polyvinylpyrrolidone polymers,        polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and        N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles        or mixtures thereof. When present in the compositions herein,        the dye transfer inhibiting agents are present at levels from        about 0.0001%, from about 0.01%, from about 0.05% by weight of        the cleaning compositions to about 10%, about 2%, or even about        1% by weight of the cleaning compositions.    -   Dispersants—The compositions of the present invention can also        contain dispersants. Suitable water-soluble organic materials        are the homo- or co-polymeric acids or their salts, in which the        polycarboxylic acid may comprise at least two carboxyl radicals        separated from each other by not more than two carbon atoms.    -   Enzymes—The compositions can comprise one or more detergent        enzymes which provide cleaning performance and/or fabric care        benefits. Examples of suitable enzymes include, but are not        limited to, hemicellulases, peroxidases, proteases, cellulases,        xylanases, lipases, phospholipases, esterases, cutinases,        pectinases, keratanases, reductases, oxidases, phenoloxidases,        lipoxygenases, ligninases, pullulanases, tannases, pentosanases,        malanases, β-glucanases, arabinosidases, hyaluronidase,        chondroitinase, laccase, and amylases, or mixtures thereof. A        typical combination is a cocktail of conventional applicable        enzymes like protease, lipase, cutinase and/or cellulase in        conjunction with amylase.    -   Enzyme Stabilizers—Enzymes for use in compositions, for example,        detergents can be stabilized by various techniques. The enzymes        employed herein can be stabilized by the presence of        water-soluble sources of calcium and/or magnesium ions in the        finished compositions that provide such ions to the enzymes.

Process of Making

The liquid detergent compositions are in the form of an aqueous solutionor uniform dispersion or suspension of surfactant, bluing agent, andcertain optional other ingredients, some of which may normally be insolid form, that have been combined with the normally liquid componentsof the composition, such as the liquid alcohol ethoxylate nonionic, theaqueous liquid carrier, and any other normally liquid optionalingredients. Such a solution, dispersion or suspension will beacceptably phase stable and will typically have a viscosity which rangesfrom about 100 to 600 cps, or from about 150 to 400 cps. For purposes ofthis invention, viscosity is measured with a Brookfield LVDV-II+viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stableliquid detergent composition. In a process for preparing suchcompositions, a liquid matrix is formed containing at least a majorproportion, or even substantially all, of the liquid components, e.g.,nonionic surfactant, the non-surface active liquid carriers and otheroptional liquid components, with the liquid components being thoroughlyadmixed by imparting shear agitation to this liquid combination. Forexample, rapid stirring with a mechanical stirrer may usefully beemployed. While shear agitation is maintained, substantially all of anyanionic surfactants and the solid form ingredients can be added.Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills, are incorporated. As a variation of the composition preparationprocedure hereinbefore described, one or more of the solid componentsmay be added to the agitated mixture as a solution or slurry ofparticles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In one aspect of forming the liquid detergent compositions, the bluingagent is first combined with one or more liquid components to form abluing agent premix, and this bluing agent premix is added to acomposition formulation containing a substantial portion, for examplemore than 50% by weight, more specifically, more than 70% by weight, andyet more specifically, more than 90% by weight, of the balance ofcomponents of the laundry detergent composition. For example, in themethodology described above, both the bluing agent premix and the enzymecomponent are added at a final stage of component additions. In anotheraspect, the bluing agent is encapsulated prior to addition to thedetergent composition, the encapsulated bluing agent is suspended in astructured liquid, and the suspension is added to a compositionformulation containing a substantial portion of the balance ofcomponents of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form.Suitable solid forms include tablets and particulate forms, for example,granular particles, flakes or sheets. Various techniques for formingdetergent compositions in such solid forms are well known in the art andmay be used herein. In one aspect, for example when the composition isin the form of a granular particle, the bluing agent is provided inparticulate form, optionally including additional but not all componentsof the laundry detergent composition. The bluing agent particulate iscombined with one or more additional particulates containing a balanceof components of the laundry detergent composition. Further, the bluingagent, optionally including additional but not all components of thelaundry detergent composition, may be provided in an encapsulated form,and the bluing agent encapsulate is combined with particulatescontaining a substantial balance of components of the laundry detergentcomposition.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingof fabrics. Generally, an effective amount of such compositions is addedto water, for example in a conventional fabric laundering automaticwashing machine, to form such aqueous laundering solutions. The aqueouswashing solution so formed is then contacted, typically under agitation,with the fabrics to be laundered therewith. An effective amount of theliquid detergent compositions herein added to water to form aqueouslaundering solutions can comprise amounts sufficient to form from about500 to 7,000 ppm of composition in aqueous washing solution, or fromabout 1,000 to 3,000 ppm of the detergent compositions herein will beprovided in aqueous washing solution.

Method of Use

Certain of the consumer products disclosed herein can be used to cleanor treat a situs inter alia a surface or fabric. Typically at least aportion of the situs is contacted with an embodiment of Applicants'consumer product, in neat form or diluted in a liquor, for example, awash liquor and then the situs may be optionally washed and/or rinsed.In one aspect, a situs is optionally washed and/or rinsed, contactedwith an aspect of the consumer product and then optionally washed and/orrinsed. For purposes of the present invention, washing includes but isnot limited to, scrubbing, and mechanical agitation. The fabric maycomprise most any fabric capable of being laundered or treated in normalconsumer use conditions. Liquors that may comprise the disclosedcompositions may have a pH of from about 3 to about 11.5. Suchcompositions are typically employed at concentrations of from about 500ppm to about 15,000 ppm in solution. When the wash solvent is water, thewater temperature typically ranges from about 5° C. to about 90° C. and,when the situs comprises a fabric, the water to fabric ratio istypically from about 1:1 to about 30:1. Employing one or more of theaforementioned methods results in a treated situs.

EXAMPLES

The following examples are provided to further illustrate the bluingagents of the present invention; however, they are not to be construedas limiting the invention as defined in the claims appended hereto. Infact, it will be apparent to those skilled in the art that variousmodifications and variations can be made in this invention withoutdeparting from the scope or spirit of the invention. All parts andpercents given in these examples are by weight unless otherwiseindicated.

Sample Preparation and Test Methods A. Sample Preparation

The following bis-azo colorant is prepared as described herein. TheUV-visible spectrum of a colorant is determined by dissolving it in asuitable solvent, typically water or methanol, at a concentration thatgives an absorbance at the lambda max of less than 1.0 at a path lengthof 1.0 cm. A Beckman Coulter DU 800 or other similar spectrophotometeris used to measure the UV-visible spectrum and determine the lambda max(“λ_(max)”) of each sample.

Example 1

To a cold (0-5° C.) solution of p-polyalkyleneoxyphenylamine (27.45grams in 100 ml of water), containing sufficient hydrochloric acid togive a pH of 1, are added 3.58 grams of sodium nitrite. The mixture isstirred for 2 hours. The mixture is then added to a cold solution of7.65 grams of 2,5-dimethoxyaniline in dilute hydrochloric acid to givean orange colored product. This product is further diazotized by addingsufficient hydrochloric acid to keep the pH at 1 followed by 3.58 gramsof sodium nitrite. After stirring 2 hours at 0-5° C., the mixture isadded to an aqueous solution of 13.96 grams of N-acetyl J acid alongwith sufficient sodium hydroxide to dissolve the N-acetyl J acid. Duringthe addition of the diazonium salt, the pH is kept at 10-12 by theaddition of aqueous sodium hydroxide solution. This resulted in a violetcolored product represented as Formula BA 1 herein.

B. Test Methods

I. Method for Determining Hueing Deposition (HD) for Dye from a WashSolution

-   -   Unbrightened multi-fiber fabric swatches are stripped prior to        use by washing at 49° C. two times with heavy duty liquid        laundry detergent nil brightener (1.55 g/L in aqueous solution).        A concentrated stock solution of each dye to be tested is        prepared in a solvent selected from dimethyl sulfoxide, ethanol        or 50:50 ethanol:water. Dye stocks are added to beakers        containing 400 mL detergent in water (heavy duty liquid laundry        detergent nil brightener, 1.55 g per liter) to produce a wash        solution with an absorbance of 0.1 AU (+0.01 AU; 1.0 cm cuvette)        at the λ_(max) of the dye. Hardness level is adjusted in the        wash and rinse to 6 gpg by addition of an appropriate volume of        10,000 gpg Ca:Mg (3:1) hardness stock solution prepared in        deionized water.    -   A 125 mL aliquot of each wash solution is placed into a separate        250 mL Erlenmeyer flask containing four swatches. The flasks are        placed on a Model 75 wrist action shaker (Burrell Scientific,        Inc., Pittsburgh, Pa.) and agitated at the maximum setting for        12 minutes, after which the wash solution is removed by        aspiration, 125 mL of rinse water (6 gpg) is added before        agitating 4 more minutes. The rinse is removed by aspiration and        the fabric swatches are spun dry (Mini Countertop Spin Dryer,        The Laundry Alternative Inc., Nashua, N.H.) for 5 minutes, then        placed in the dark to dry.    -   L*, a*, and b* values for cotton, nylon and polyester are        measured on the dry swatches using a LabScan XE reflectance        spectrophotometer (HunterLabs, Reston, Va.; D65 illumination,        10° observer, UV light excluded). The L*, a*, and b* values of        the 4 swatches generated for each dye are averaged and the        hueing deposition (HD) of each dye is calculated for each fabric        type using the following equation:

HD=DE*=((L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²)^(1/2)

wherein the subscripts c and s respectively refer to the control, i.e.,the fabric washed in detergent with no dye, and the sample, i.e., thefabric washed in detergent containing dye.

II. Method for Determining Cotton to Nylon Selectivity Ratio

-   -   The selectivity ratio parameter is calculated only when at least        one of the individual deposition (HD) values for cotton or        polyamide is ≥2.0. The Cotton to Nylon Selectivity Ratio (SR) is        calculated using the following:

SR=Cotton HD/Nylon HD

III. Method for Determining Absolute Hue Angle (θ_(A))

-   -   The L*, a*, and b* values of the four swatches generated for a        dye from Test Method I are averaged and the a* value and b*        value for cotton is used to determine the absolute hue angle for        said dye. Typical color descriptors associated with such hue        angles are 90° (yellow), 180° (green), 270° (blue), and 360° or        0° (red),    -   The absolute hue angle is calculated using the following formula        in Microsoft Excel:

=IF(B1<0,360+DEGREES(A TAN 2(A1,B1)),DEGREES(A TAN 2(A1,B1)))

-   -   where B1 refers to the cell containing the average b* value and        A1 refers to the cell containing the average a* value.

EXAMPLES Performance Example

-   -   The performance of nine different bis-azo bluing agents, three        comparative and six inventive, are tested and Hueing Deposition,        and Selectivity Ratio are assessed according to the equations        disclosed above in the methods. The results are given in the        Table immediately below.

Test Results

Selectivity Ratio (ΔE*_(Cotton)/ Dye ΔE*_(Cotton) ΔE*_(Nylon)ΔE*_(Nylon))

29.24 19.36 1.51

19.26 14.91 1.29

12.03 21.15 0.57

19.81 5.32 3.72

24.57 6.58 3.73

24.57 4.33 5.67

23.07 3.79 6.09

7.26 0.49 14.8

6.82 1.66 4.10

All the dyes show some level of deposition on cotton and nylon, TheSelectivity Ratio (SR) for the comparative bis-azo bluing agents liewithin a range of 0.5 to about 1.5. Substituting an acetyl or H for thephenyl ring in N-phenyl J-acid increases the SR to above 3.5 and above5.5, respectively. Moreover, replacing the J-acid moiety with an H-acidor chromotropic acid group also leads to improved SR values.

-   -   Thus the compositions and methods of the invention provide good        deposition on cellulosic fabrics, and improved selectivity        ratios, avoiding problematic overhueing even on synthetic        fabrics such as nylon.

Exemplary Detergent Formulations Formulations 1a-1l: Liquid DetergentFormulations

Tables 4A and 4B provide examples of liquid detergent formulations whichinclude at least one bluing agent of the present invention. Theformulations are shown in Table 4A as Formulations 1a through 1f and inTable 4B as Formulations 1g through 1l.

TABLE 4A Liquid Detergent Formulations Comprising the Inventive BluingAgent 1a 1b 1c 1d 1e 1f⁵ Ingredient wt % wt % wt % wt % wt % wt % sodiumalkyl  14.4%  14.4%  9.2%   5.4% ether sulfate linear   4.4%  4.4% 12.2%  5.7%   1.3%  22.0% alkylbenzene sulfonic acid alkyl   2.2%  2.2% 8.8%  8.1%   3.4%  18.0% ethoxylate amine oxide   0.7%  0.7%  1.5%citric acid   2.0%  2.0%  3.4%  1.9%   1.0%  1.6% fatty acid   3.0% 3.0%  8.3%  16.0% protease   1.0%  1.0%  0.7%  1.0%  2.5% amylase  0.2%  0.2%  0.2%  0.3% lipase  0.2% borax   1.5%  1.5%  2.4%  2.9%calcium and   0.2%  0.2% sodium formate formic acid  1.1% amine   1.8% 1.8%  2.1%  3.2% ethoxylate polymers sodium   0.2% polyacrylate sodium 0.6% polyacrylate copolymer DTPA¹   0.1%  0.1%  0.9% DTPMP²  0.3% EDTA³  0.1% fluorescent  0.15%  0.15%  0.2%  0.12%  0.12%  0.2% whiteningagent ethanol   2.5%  2.5%  1.4%  1.5% propanediol   6.6%  6.6%  4.9% 4.0%  15.7% sorbitol  4.0% ethanolamine   1.5%  1.5%  0.8%  0.1%  11.0%sodium   3.0%  3.0%  4.9%  1.9%   1.0% hydroxide sodium  2.0% cumenesulfonate silicone suds  0.01% suppressor perfume   0.3%  0.3%  0.7% 0.3%   0.4%  0.6% Non-tinting 0.0001% 0.001% 0.008%  0.03%  0.015% 0.05% dyes⁴ First bis-azo 0.001% 0.001% 0.0005% colorant⁶ Second bis- 0.013% 0.005% 0.003% 0.001% azo colorant⁶ water balance balance balancebalance balance balance  100.0% 100.0% 100.0% 100.0%  100.0% 100.0%

TABLE 4B Liquid Detergent Formulations Comprising the Inventive BluingAgent 1g 1h 1i 1j 1k 1l⁵ Ingredient wt % wt % wt % wt % wt % wt % sodiumalkyl  14.4%  14.4%  9.2%  5.4% ether sulfate linear   4.4%  4.4%  12.2% 5.7%  1.3%  22.0% alkylbenzene sulfonic acid alkyl   2.2%  2.2%  8.8% 8.1%  3.4%  18.0% ethoxylate amine oxide   0.7%  0.7%  1.5% citric acid  2.0%  2.0%  3.4%  1.9%  1.0%  1.6% fatty acid   3.0%  3.0%  8.3% 16.0% protease   1.0%  1.0%  0.7%  1.0%  1.7% amylase   0.2%  0.2% 0.2%  0.6% lipase  0.2%  0.2% borax   1.5%  1.5%  2.4%  2.9% calciumand   0.2%  0.2% sodium formate formic acid  1.1% amine   1.8%  1.8% 2.1%  3.2% ethoxylate polymers sodium  0.2% polyacrylate sodium  0.6%polyacrylate copolymer DTPA¹   0.1%  0.1%  0.9% DTPMP²  0.3% EDTA³  0.1%fluorescent  0.15%  0.15%  0.2%  0.12%  0.12%  0.2% whitening agentethanol   2.5%  2.5%  1.4%  1.5% propanediol   6.6%  6.6%  4.9%  4.0% 15.7% sorbitol  4.0% ethanolamine   1.5%  1.5%  0.8%  0.1%  11.0%sodium   3.0%  3.0%  4.9%  1.9%  1.0% hydroxide sodium  2.0% cumenesulfonate silicone suds  0.01% suppressor perfume   0.3%  0.3%  0.7% 0.3%  0.4%  0.6% Non-tinting 0.0001% 0.001% 0.008%  0.03% 0.015%  0.05%dyes⁴ First bis-azo  0.01% 0.005% 0.005% colorant⁶ Second bis-  0.01% 0.02% 0.003% 0.012% azo colorant⁶ opacifier⁷  0.5% water balancebalance balance balance balance balance  100.0% 100.0% 100.0% 100.0%100.0% 100.0%

Footnotes for Formulations 1a-l: ¹diethylenetriaminepentaacetic acid,sodium salt²diethylenetriaminepentakismethylenephosphonic acid, sodiumsalt³ethylenediaminetetraacetic acid, sodium salt⁴a non-tinting dye ormixture of non-tinting dyes used to adjust formula color⁵compactformula, packaged as a unitized dose in polyvinyl alcohol film⁶Bis-azocolorants selected from BA1-35⁷Acusol OP301

Formulations 2a-2e: Granular Detergent Formulations

Table 5 provides examples of granular detergent formulations whichinclude at least one bluing agent of the present invention. Theformulations are shown in Table 5 as Formulations 2a through 2e.

TABLE 5 Granular Detergent Formulations Comprising the Inventive BluingAgent Ingredient 2a 2b 2c 2d 2e wt % wt % wt % wt % wt % Na linearalkylbenzene  3.4%  3.3%  11.0%  3.4%  3.3% sulfonate Na alkylsulfate 4.0%  4.1%  4.0%  4.1% Na alkyl sulfate  9.4%  9.6%  9.4%  9.6%(branched) alkyl ethoxylate  3.5% type A zeolite  37.4%  35.4%  26.8% 37.4%  35.4% sodium carbonate  22.3%  22.5%  35.9%  22.3%  22.5% sodiumsulfate  1.0%  18.8%  1.0% sodium silicate  2.2% protease  0.1%  0.2% 0.1%  0.2% sodium polyacrylate  1.0%  1.2%  0.7%  1.0%  1.2%carboxymethylcellulose  0.1% PEG 600  0.5%  0.5% PEG 4000  2.2%  2.2%DTPA  0.7%  0.6%  0.7%  0.6% fluorescent whitening  0.1%  0.1%  0.1% 0.1%  0.1% agent sodium percarbonate  5.0%  5.0% sodium nonanoyloxy- 5.3%  5.3% benzenesulfonate silicone suds suppressor  0.02%  0.02% 0.02%  0.02% perfume  0.3%  0.3%  0.2%  0.3%  0.3% First bis-azocolorant¹ 0.004% 0.001%  0.02% Second bis-azo colorant¹ 0.006% 0.002%0.004% water and miscellaneous balance balance Balance balance balance100.0% 100.0% 100.0% 100.0% 100.0% ¹Bis-azo colorants selected fromBA1-35.

Exemplary Fabric Care Compositions Formulations 3a-3d: Liquid FabricCare Compositions

Table 6 provides examples of liquid fabric care compositions whichinclude at least one bluing agent of the present invention. Thecompositions are shown in Table 6 as Formulations 3a through 3d.

TABLE 6 Liquid Fabric Care Compositions Comprising the Inventive BluingAgent Ingredients 3a 3b 3c 3d Fabric Softening Active ^(a) 13.70% 13.70%13.70% 13.70% Ethanol  2.14%  2.14%  2.14%  2.14% Cationic Starch ^(b) 2.17%  2.17%  2.17%  2.17% Perfume  1.45%  1.45%  1.45%  1.45% PhaseStabilizing Polymer ^(c)  0.21%  0.21%  0.21%  0.21% Calcium Chloride0.147% 0.147% 0.147% 0.147% DTPA ^(d) 0.007% 0.007% 0.007% 0.007%Preservative ^(e)  5 ppm  5 ppm  5 ppm  5 ppm Antifoam ^(f) 0.015%0.015% 0.015% 0.015% First bis-azo colorant^(i) 30 ppm 15 ppm Secondbis-azo colorant^(i) 30 ppm Third bis-azo colorant^(i) 30 ppm 15 ppmTinopal CBS-X ^(g) 0.2 0.2 0.2 0.2 Ethoquad C/25 ^(h) 0.26 0.26 0.260.26 Ammonium Chloride  0.1%  0.1%  0.1%  0.1% Hydrochloric Acid 0.012%0.012% 0.012% 0.012% Deionized Water Balance Balance Balance Balance^(a) N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride. ^(b)Cationic starch based on common maize starch or potato starch,containing 25% to 95% amylose and a degree of substitution of from 0.02to 0.09, and having a viscosity measured as Water Fluidity having avalue from 50 to 84. ^(c) Copolymer of ethylene oxide and terephthalatehaving the formula described in U.S. Pat. No. 5,574,179 at col. 15,lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R^(l) isessentially 1,4-phenylene moieties, each R² is essentially ethylene,1,2-propylene moieties, or mixtures thereof. ^(d)Diethylenetriaminepentaacetic acid. ^(e) KATHON ® CG available from Rohmand Haas Co. ^(f) Silicone antifoam agent available from Dow CorningCorp. under the trade name DC2310. ^(g) Disodium4,4′-bis-(2-sulfostyryl) biphenyl, available from Ciba SpecialtyChemicals. ^(h) Cocomethyl ethoxylated [15] ammonium chloride, availablefrom Akzo Nobel. ^(i)Bis-azo colorants selected from BA1-35.

Accordingly, the present invention provides a bluing agent for textileand/or paper substrates comprising at least one chromophore componentthat comprises a bis-azo colorant and at least one polymeric component.A laundry detergent composition and a rinse added fabric softenercontaining such a bluing agent is also contemplated herein.

While particular aspects of the present invention have been illustratedand described, it would be obvious to those skilled in the art thatvarious other changes and modifications can be made without departingfrom the spirit and scope of the invention. It is therefore intended tocover in the appended claims all such changes and modifications that arewithin the scope of this invention.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

We claim:
 1. A treated situs comprising: (a) a textile substrate; and(b) a bluing agent, wherein the bluing agent is comprised of: (i) atleast one chromophore component that comprises a bis-azo colorant, and(ii) at least one polymeric component; wherein said chromophore and saidpolymeric component are covalently bound to one another and wherein thebluing agent is selected from the following structures:

and mixtures thereof; wherein R¹ is a polyoxyalkylene chain having from2 to 100 repeating units; R² and R³ are independently selected from thegroup consisting of H, alkyl, alkoxy, alkyleneoxy, capped alkyleneoxy,polyalkyleneoxy and capped polyalkyleneoxy; R⁴ is selected from H, C(O)Hand C(O)R⁵; wherein R⁵ is independently selected from the groupconsisting of C₁₋₇ alkyl, C₆₋₁₀ aryl, and C₇₋₁₁ arylalkyl; wherein saidcapping groups are independently selected from C(O)R⁵ and R⁵; whereinthe A ring may be further substituted with one or more groups selectedfrom the group consisting of C₁₋₈ alkyl, C₁₋₈ alkoxy, nitro and OR⁶;wherein R⁶ is selected from the group consisting of H, hydroxyalkyl, apolyalkyleneoxy and a capped polyalkyleneoxy; wherein each M isindependently selected from the group consisting of an alkali metalcation, an ammonium ion and an alkaline earth metal cation.
 2. A treatedsitus according to claim 1 in which in the bluing agent R² and R³ areindependently selected from the group consisting of H, alkyl, alkoxy,alkyleneoxy, and capped alkyleneoxy.
 3. A treated situs according toclaim 1 in which in the bluing agent, R² and R³ are independentlyselected from the group consisting of H, C₁₋₄ alkyl, and C₁₋₄ alkoxy. 4.A treated situs according to claim 1 in which in the bluing agent, R¹ isa polyoxyalkylene chain having from 4 to 50 repeating units.
 5. Atreated situs according to claim 1, wherein the polyoxyalkylene chaincomprises ethyleneoxide for at least 50% of the units.
 6. A treatedsitus according to claim 1 wherein the bluing agent's chromophoreexhibits an absorbance spectrum maximum in water of from about 560nanometers to about 640 nanometers.
 7. A treated situs according toclaim 1 wherein the bluing agent exhibits an absolute hue angle in therange of 220° to
 3200. 8. A treated situs according to claim 5 whereinR² is alkyl and R³ is selected from C₁₋₄ alkyl and C₁₋₄ alkoxy groups.9. A treated situs according to claim 5 wherein R² and R³ are C₁₋₄alkoxy groups.
 10. A treated situs according to claim 9, wherein R⁴ is Hor C(O)CH₃.
 11. A treated situs according to claim 10, wherein R⁴ is Hor C(O)CH₃.
 12. A treated situs according to claim 3, wherein the A ringis substituted with another group selected from alkyl, alkoxy and OR¹.13. A treated situs according to claim 1 wherein the bluing agentexhibits an absolute hue angle in the range of 240° to 310°.
 14. Atreated situs according to claim 1 wherein the bluing agent exhibits anabsolute hue angle in the range of 250° to 300°.
 15. A treated situsaccording to claim 1 wherein the textile substrate a fabric.
 16. Atreated situs according to claim 15 wherein the fabric is comprised offiber selected from the group consisting of cellulose, polyester, andpolyamide.
 17. A treated situs according to claim 16 wherein celluloseis cotton.
 18. A treated situs according to claim 16 wherein polyamideis nylon.